Glass comprising solid electrolyte particles and lithium battery

ABSTRACT

A method for producing a solid electrolyte, comprising: grinding raw materials comprising lithium sulfide and phosphorus sulfide in a hydrocarbon solvent, optionally comprising stirring a slurry comprising the raw materials and the hydrocarbon solvent in a reaction vessel, and optionally, circulating the slurry through a connecting pipe, wherein the method is carried out in an apparatus comprising the grinder, the reaction vessel and the connecting pipe that connects the grinder and the reaction vessel.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a divisional of U.S. patent application Ser.No. 14/680,514, filed on Apr. 7, 2015, which is a divisional of U.S.patent application Ser. No. 13/260,054, filed on Sep. 23, 2011, the textof which is incorporated by reference, which is a National Stage entryunder 35 U. S. C. 371 of PCT/JP 10/002538, filed on Apr. 7, 2010 andclaims priority to Japanese Patent Application No. 2009-096482, filed onApr. 10, 2009.

TECHNICAL FIELD

The invention relates to glass that includes solid electrolyteparticles, a glass ceramic, and a lithium battery using the same.

BACKGROUND ART

In recent years, a high-performance lithium secondary battery or thelike has been increasingly demanded for a portable information terminal,a portable electronic instrument, a domestic small power storage device,a motorcycle, an electric vehicle, and a hybrid electric vehicle thatutilize a motor as the power source, and the like. The term “secondarybattery” refers to a battery that can be charged and discharged. Asecondary battery has been used in a wide variety of applications, and afurther improvement in safety and performance has been desired.

An electrolyte that exhibits high lithium ion conductivity at roomtemperature has been generally limited to an organic electrolyte. Anorganic electrolyte is flammable due to inclusion of an organic solvent.Therefore, leakage or ignition may occur when using an ion-conductivematerial containing an organic solvent as an electrolyte for a battery.Moreover, since the organic electrolyte is liquid, conduction of counteranions occurs in addition to conduction of lithium ions. Therefore, thelithium ion transport number is equal to or less than “1”.

An inorganic solid electrolyte is nonflammable, and is highly safe ascompared with the organic electrolyte which is usually used. However,since the electrochemical performance of the inorganic solid electrolyteis inferior to some extent as compared with the organic electrolyte, itis necessary to further improve the performance of the inorganic solidelectrolyte.

In view of the above situation, a sulfide solid electrolyte has beenextensively studied.

For example, sulfide glass having an ion conductivity of 10⁻³ S/cm(e.g., LiI—Li₂S—P₂S₅, LiI—Li₂S—B₂S₃, and LiI—Li₂S—SiS₂) was discoveredin the 1980's as a lithium-ion-conductive solid electrolyte having highionic conductivity.

These electrolytes are normally solids, and ground (homogenized) bymilling to obtain solid electrolyte particles (Patent Document 1). Anelectrolyte may also be obtained by a heat melting method at a hightemperature (Patent Document 2).

RELATED-ART DOCUMENT Patent Document

Patent Document 1: JP-A-2004-265685

Patent Document 2: JP-A-2008-4334

SUMMARY OF THE INVENTION

The homogeneity of the surface of the electrolyte is important forstabilizing the performance of the battery (end product). Since thesurface of the electrolyte is a medium where lithium ions move directly,the resistance may increase partially if the homogeneity of the surfaceof the electrolyte is poor, so that a stable battery performance may notbe obtained. When producing a glass ceramic, a crystal that exhibitsexcellent conductivity may not be formed partially if the homogeneity ispoor, so that the battery performance may deteriorate when theelectrolyte is incorporated in the battery. Therefore, solid electrolyteparticles having improved homogeneity have been desired.

An object of the invention is to stabilize the performance of a lithiumsecondary battery by eliminating inhomogeneity of the surface of glass.

The inventors of the invention conducted extensive studies, and foundthat glass obtained by a specific production method exhibits highhomogeneity. This finding has led to the completion of the invention.

The invention provides the following glass and the like.

1. Glass including an aggregate of solid electrolyte particles includingLi, P, and S, where in when a Raman spectrum of the glass is repeatedlymeasured and a peak at 330 to 450 cm⁻¹ in each Raman spectrum isseparated to waveforms of individual components, a standard deviation ofa wave form area ratio of each component is less than 4.0 (e.g., 0.5 ormore and less than 4.0).2. The glass according to 1, wherein the area ratios of PS₄ ³⁻, P₂S₇ ⁴⁻,and P₂S₆ ⁴⁻ in Raman spectrum are 15 to 65%, 25 to 80%, and 5 to 30%,respectively.3. The glass according to 1 or 2, wherein the solid electrolyteparticles have a maximum particle size of 20 μm or less.4. Glass produced by alternately performing the step of reacting rawmaterials including at least lithium sulfide and other sulfides in ahydrocarbon solvent while grinding the raw materials, and the step ofreacting the raw materials including at least lithium sulfide and othersulfides in a hydrocarbon solvent.5. Glass produced by reacting raw materials including at least lithiumsulfide and other sulfides in a hydrocarbon solvent.6. A glass ceramic obtained by heating the glass according to any one of1 to 5.7. A lithium battery including an electrolyte layer, a positiveelectrode, and a negative electrode, at least one of the electrolytelayer, the positive electrode and the negative electrode including atleast one of the glass according to any one of 1 to 5 and the glassceramic according to 6.8 An apparatus including the lithium battery according to 7.

According to the invention, it is possible to stabilize the performanceof a lithium secondary battery by eliminating inhomogeneity of thesurface of glass.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the Raman spectrum of glass obtained in Example 1.

FIG. 2 is a view showing a state in which the peak in the Raman spectrumof glass obtained in Example 1 is separated to waveforms.

FIG. 3 shows a scanning electron microscope (SEM) photograph of theglass powder obtained in Example 3.

FIG. 4 is a view showing an example of an apparatus that may be used forthe production method according to the invention.

FIG. 5 is a view showing another example of an apparatus that may beused for the production method according to the invention.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Glass according to the invention includes an aggregate of solidelectrolyte particles including Li, P, and S, wherein when a Ramanspectrum of the glass is repeatedly measured, and a peak at 330 to 450cm⁻¹ in each Raman spectrum is separated to waveforms of individualcomponents, a standard deviation of a waveform area ratio of eachcomponent being less than 4.0. The glass exhibits excellent homogeneitywhen the standard deviation of the waveform area ratio of each componentis less than 4.0.

The Raman spectrum is used to determine the state of a solid, a powder,or the like (see Japanese Patent No. 3893816, Japanese Patent No.3893816, Japanese Patent No. 3929303, Japanese Patent No. 3979352, andJapanese Patent No. 4068225, for example). The Raman spectrum issuitably used when analyzing the surface state of a solid. Even ifparticles from the same lot are measured, when the composition of theirsurface is inhomogenous, a different spectrum is obtained. For example,when subjecting a solid material to mechanical milling, if part of thesolid material has been sufficiently ground, and another part of thesolid material has not been sufficiently ground and adheres to the wall,the reproducibility of the spectrum is adversely affected due to adecrease in homogeneity. Since the Raman spectrum is an index of ahomogeneous material, the invention utilizes the reproducibility of thespectrum (particularly the variance value) as an index.

FIG. 1 shows an example of the Raman spectrum of the glass according tothe invention. The Raman spectrum measurement conditions used herein aredescribed in the examples. As shown in FIG. 1, a characteristic peak isdetected at around 400 cm⁻¹. Since the peak is unsymmetrical, the peakis a composite peak of a plurality of components. The peak is identifiedas a three-component composite peak of PS₄ ³⁻, P₂S₇ ⁴⁻, and P₂S₆ ⁴⁻ (M.Tachez, J. -P. Malugani, R. Mercier, and G. Robert, Solid State Ionics,14, 181 (1984)). It is desirable to individually detect the peak using ahigh-resolution system. However, even if the peak is not sufficientlyseparated, it is possible to separate the peak into individual peaksusing common or dedicated waveform analysis software. FIG. 2 shows theresults when separating the peak into individual peaks using waveformseparation software (the dotted line in FIG. 2 indicates the originalpeak). The area ratio of each component can be calculated using thismethod.

The standard deviation can be calculated from the above-mentioned areavalue using a general calculation method.

It is desirable to measure the Raman spectrum five or more times whilechanging the measurement sample tube or changing the measurementposition of an identical measurement sample tube.

Note that the Raman spectrum was measured five times in the exampleswhile changing the measurement position of an identical measurementsample tube.

If the standard deviation of the area ratio of the waveform thatindicates each of PS₄ ³⁻, P₂S₇ ⁴⁻, and P₂S₆ ⁴⁻ is less than 4.0, thesurface of each glass particle is homogeneous, and the performance of abattery produced using the glass particles is stabilized.

The standard deviation is preferably 3.5 or less, and more preferably3.0 or less.

The standard deviation of the area ratio of the waveform that indicatesPS₄ ³⁻ is preferably 3.0 or less. The standard deviation of the arearatio of the waveform that indicates P₂S₇ ⁴⁻ is preferably 2.5 or less.The standard deviation of the area ratio of the waveform that indicatesP₂S₆ ⁴⁻ is preferably 2.0 or less. The standard deviation of the arearatio of the waveform that indicates PS₄ ³⁻ is more preferably 2.5 orless. The standard deviation of the area ratio of the waveform thatindicates P₂S₇ ⁴⁻ is more preferably 2.0 or less. The standard deviationof the area ratio of the waveform that indicates P₂S₆ ⁴⁻ is morepreferably 1.5 or less.

The area ratios of PS₄ ³⁻, P₂S₇ ⁴⁻, and P₂S₆ ⁴⁻ in the Raman spectrumare preferably 15 to 65%, 25 to 80%, and 5 to 30%, and more preferably20 to 55%, 35 to 75%, and 5 to 25%, respectively. Since the P₂S₆ ⁴⁻component has inferior lithium ion conductivity as compared with theother components, the battery performance is more improved when the P₂S₆⁴⁻ content is lower.

The maximum particle size of the solid electrolyte particles that formthe glass according to the invention, determined by observing an SEMphotograph thereof, is preferably 20 μm or less, and more preferably 15μm or less. The term “maximum particle size” used herein refers to themaximum linear distance from the surface of a particle to anothersurface of the particle. If large particles having a particle size ofmore than 20 μm are present, the uniformity (homogeneity) achieved whenforming a sheet may be (adversely) affected. The presence of largeparticles may cause a variation in heat transfer during a heattreatment, may hinder fusion bonding, and may cause defects.

The number average particle size of the solid electrolyte particles ispreferably 10 μm or less, and more preferably 8 μm or less.

If the solid electrolyte particles have a large particle size, it may benecessary to increase the thickness of the electrolyte layer of thebattery.

A homogeneous electrolyte may also be confirmed by a DSC pattern. Aninhomogeneous electrolyte normally shows a bimodal peak pattern or awide half-width temperature range. A homogeneous electrolyte shows asingle peak and a narrow half-width temperature range. The glassaccording to the invention normally has a peak temperature between 225°C. and 270° C. and a half-width temperature of 10° C. or less(particularly 5° C. or less). The measurement method is described in theexamples.

The solid electrolyte that forms the glass according to the inventionincludes Li, P, and S. The sulfide-based solid electrolyte includes Li,P, and S as the main components. The solid electrolyte may include onlyLi, P, and S, or may further include an additional substance such as Al,B, Si, and Ge.

The homogenous glass according to the invention may be produced byreacting raw materials including lithium sulfide and other sulfides in ahydrocarbon solvent. Specifically, the glass according to the inventionis, unlike conventional methods, produced without using mechanicalmilling, or without rapidly cooling the raw materials melted by heating.

Mechanical milling may cause the particles present on the wall and theballs inside the mill to have an inhomogenous surface state. Whenrapidly cooling the raw materials melted by heating to form glass, andgrinding the glass to obtain glass particles, the glass particles aredifficult to have a homogeneous surface.

The temperature when causing the raw materials to come in contact witheach other in the hydrocarbon solvent is normally 80 to 300° C.,preferably 100 to 250° C., and more preferably 100 to 200° C. Thecontact (reaction) time is normally 5 minutes to 50 hours, andpreferably 10 minutes to 40 hours.

Note that temperature and time may be combined according to conditions.

It is preferable to stir the raw materials when causing the rawmaterials to come in contact with each other. It is preferable to stirthe raw materials in an inert gas atmosphere (e.g., nitrogen or argon).The dew point of the inert gas is preferably −20° C. or less, andparticularly preferably −40° C. or less. The pressure is normallyordinary pressure to 100 MPa, and preferably ordinary pressure to 20MPa.

The solid electrolyte may be produced using general-purpose equipment(e.g., reaction vessel or autoclave) in the method. Specifically,special equipment such as equipment that withstands a high temperatureis unnecessary. The amount of solvent that remains in the solidelectrolyte can be reduced by utilizing the hydrocarbon solvent.

The glass according to the invention may also be produced by alternatelyperforming the step of reacting raw materials including lithium sulfideand other sulfides in a hydrocarbon solvent while grinding the rawmaterials, and the step of reacting the raw materials including lithiumsulfide and other sulfides in a hydrocarbon solvent.

For example, the raw materials are reacted in a grinder while grindingthe raw materials to synthesize a solid electrolyte, the raw materialsare separately reacted in a hydrocarbon solvent in a reaction vessel tosynthesize a solid electrolyte, and the raw materials during thereaction are circulated between the grinder and the reaction vessel.

FIG. 4 shows an example of an apparatus that may be used for theproduction method according to the invention.

In an apparatus 1 shown in FIG. 4, the hydrocarbon solvent and the rawmaterials are supplied to a grinder 10 and a reaction vessel 20. Hotwater is supplied to (HW) and discharged from (RHW) a heater 30. Thetemperature inside the grinder 10 is kept using the heater 30, and theraw materials are reacted while grinding the raw materials in thehydrocarbon solvent to synthesize a solid electrolyte. The temperatureinside the reaction vessel 20 is kept using an oil bath 40, and the rawmaterials are reacted in the hydrocarbon solvent to synthesize a solidelectrolyte. The temperature inside the reaction vessel 20 is measuredusing a thermometer (Th). The reaction system is stirred by rotating astirring blade 24 using a motor (M) so that a slurry formed by the rawmaterials and the solvent does not precipitate. Cooling water issupplied to (CW) and discharged from (RCW) a cooling tube 26. Thecooling tube 26 cools and liquefies the solvent vaporized in a container22, and returns the solvent to the container 22. When synthesizing thesolid electrolyte in the grinder 10 and the reaction vessel 20, the rawmaterials during the reaction are circulated by a pump 54 between thegrinder 10 and the reaction vessel 20 through connecting pipes 50 and52. The temperature of the raw materials and the solvent supplied to thegrinder 10 is measured using a thermometer (Th) provided to the secondconnecting pipe on the upstream side of the grinder 10.

Examples of the grinder 10 include a rotary mill (a tumbling mill), aswing mill, a vibration mill, and a bead mill. It is preferable to use abead mill since the raw materials can be finely ground. The reactivityof the raw materials increases as the size of the raw materialsdecreases, so that the solid electrolyte can be produced within a shorttime.

When the grinder includes balls, it is preferable that the balls be madeof zirconium, reinforced alumina, or alumina in order to prevent asituation in which the materials of the balls and the container aremixed into the solid electrolyte due to wear. In order to prevent asituation in which the balls enter the reaction vessel 20 from thegrinder 10, a filter that separates the balls from the raw materials andthe solvent may optionally be provided in the grinder 10 or the firstconnecting pipe 50.

The grinding temperature in the grinder is preferably 20° C. or more and90° C. or less, and more preferably 20° C. or more and 80° C. or less.If the grinding temperature in the grinder is less than 20° C. theeffect of reducing the reaction time may be small. If the grindingtemperature in the grinder exceeds 90° C., the strength of zirconia,reinforced alumina, or alumina used as the material for the containerand the balls may significantly decrease, whereby wear or deteriorationof the container and the balls may occur, or the electrolyte may becontaminated.

The reaction temperature in the container 22 is preferably 60° C. to300° C. The reaction temperature in the container 22 is more preferably80° C. to 200° C. If the reaction temperature in the container 22 isless than 60° C., the vitrification reaction may take time, so that asufficient production efficiency may not be achieved. If the reactiontemperature in the container 22 exceeds 300° C. undesirable crystals maybe deposited.

It is preferable to employ a high temperature since the reaction rateincreases at a high temperature. However, when increasing thetemperature of the grinder, mechanical problems (e.g., wear) may occur.Therefore, it is preferable to set the reaction temperature in thereaction vessel at a high temperature, and maintain the temperature inthe grinder at a relatively low temperature.

The reaction time is normally 5 minutes to 50 hours, and preferably 10minutes to 40 hours.

As shown in FIG. 5, a heat exchanger 60 (heat-exchange means) may beprovided to the second connecting pipe 52, and the high-temperature rawmaterials and solvent discharged from the reaction vessel 20 may becooled, and then supplied to the grinder 10.

In the above production method, it is preferable to use Li₂S and othersulfides as the raw materials. One or more sulfides selected fromphosphorus sulfide, silicon sulfide, boron sulfide, germanium sulfide,and aluminum sulfide are preferable as the sulfides mixed with Li₂S. Itis particularly preferable to use P₂S₅.

Lithium sulfide is preferably used in an amount of 30 to 95 mol %, morepreferably 40 to 90 mol %, and particularly preferably 50 to 85 mol %,based on the total amount of lithium sulfide and other sulfides.

Lithium sulfide (Li₂S) and phosphorus pentasulfide (P₂S₅), or lithiumsulfide, phosphorus, and sulfur, or lithium sulfide, phosphoruspentasulfide, phosphorus, and/or sulfur are normally used.

When mixed, the molar ratio of lithium sulfide to phosphoruspentasulfide, or phosphorus and sulfur is normally 50:50 to 80:20, andpreferably 60:40 to 75:25. The molar ratio “Li₂S:P₂S₅” is particularlypreferably about 70:30.

Examples of the hydrocarbon solvent include saturated hydrocarbons,unsaturated hydrocarbons, aromatic hydrocarbons, and the like. Examplesof the saturated hydrocarbons include hexane, pentane, 2-ethylhexane,heptane, octane, decane, cyclohexane, methylcyclohexane, IP Solvent 1016(manufactured by Idemitsu Kosan Co., Ltd.), IP Solvent 1620(manufactured by Idemitsu Kosan Co., Ltd.), and the like. Examples ofthe unsaturated hydrocarbons include hexene, heptene, cyclohexene, andthe like.

Examples of the aromatic hydrocarbons include toluene, xylene,ethylbenzene, decalin, 1,2,3,4-tetrahydronaphthalene, and mixed solventssuch as Ipzole 100 (manufactured by Idemitsu Kosan Co., Ltd.) and Ipzole150 (manufactured by Idemitsu Kosan Co., Ltd.). Among these, toluene,xylene, ethylbenzene, and Ipzole 150 are preferable.

It is preferable that the water content in the hydrocarbon solvent be 50ppm (weight) or less taking account of a reaction with the raw materialsulfide and the synthesized solid electrolyte. The sulfide-based solidelectrolyte may be modified due to a reaction with water, so that theperformance of the solid electrolyte may deteriorate. Therefore, it ispreferable that the water content in the hydrocarbon solvent be as lowas possible (more preferably 30 ppm or less, and still more preferably20 ppm or less).

An additional solvent may optionally be added to the hydrocarbonsolvent. Specific examples of the additional solvent include ketonessuch as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran,alcohols such as ethanol and butanol, esters such as ethyl acetate,halogenated hydrocarbons such as dichloromethane and chlorobenzene, andthe like.

The organic solvent is preferably used in such an amount that lithiumsulfide and other sulfides (raw materials) form a solution or a slurrywhen the solvent is added. The raw materials are normally added in atotal amount of about 0.03 to 1 kg based on 1 kg of the solvent. The rawmaterials are preferably added in a total amount of 0.05 to 0.5 kg, andparticularly preferably 0.1 to 0.3 kg based on 1 kg of the solvent.

The reaction product is dried, and the solvent is removed to obtainsulfide glass.

The ion conductivity of the sulfide-based solid electrolyte can beimproved by heating the resulting glass normally at 200° C. or more and400° C. or less, and preferably 250 to 320° C. This is because thesulfide-based solid electrolyte (glass) is converted into sulfidecrystallized glass (glass ceramic). The heating time is preferably 1 to5 hours, and particularly preferably 1.5 to 3 hours.

Note that heating in the drying step and heating in the crystallizationstep may be performed by a single heating step.

The glass or the glass ceramic according to the invention may be used asa solid electrolyte layer of an all-solid-state lithium secondarybattery, a solid electrolyte to be mixed into a positive electrodematerial or a negative electrode material, or the like. A lithiumbattery according to the invention includes an electrolyte layer, apositive electrode, a negative electrode, and at least one of theelectrolyte layer, the positive electrode and the negative electrodeincludes the glass or the glass ceramic according to the invention thatis included in one or more of the electrolyte layer, the positiveelectrode, and the negative electrode.

EXAMPLES Production Example 1

(1) Production of Lithium Sulfide

Lithium sulfide was produced by the method according to the firstembodiment (two-step method) disclosed in JP-A-7-330312. Specifically, a10-liter autoclave equipped with a stirring blade was charged with3326.4 g (33.6 mol) of N-methyl-2-pyrrolidone (NMP) and 287.4 g (12 mol)of lithium hydroxide. The mixture was heated to 130° C. with stirring(300 rpm). After heating, hydrogen sulfide was bubbled into the mixturefor 2 hours at a rate of 3 L/min. The temperature of the reactionsolution was increased in a nitrogen stream (200 cc/min) to desulfurizeand hydrogenate the reacted lithium hydrosulfide and obtain lithiumsulfide. Water produced by the reaction between hydrogen sulfide andlithium hydroxide as a by-product started to evaporate as thetemperature of the reaction solution increased. The evaporated water wascondensed using a condenser, and removed from the system. Thetemperature of the reaction solution increased when water was distilledaway from the system. The temperature rising operation was stopped whenthe temperature reached 180° C., and the system was maintained at aconstant temperature. After completion of desulfurization andhydrogenation (about 80 minutes), the reaction was terminated to obtainlithium sulfide.

(2) Purification of Lithium Sulfide

After decanting NMP in 500 mL of the slurry reaction solution(NMP-lithium sulfide slurry) obtained in (1), 100 mL of dehydrated NMPwas added to the reaction solution. The mixture was stirred at 105° C.for about 1 hour. NMP was decanted at 105° C. After the addition of 100mL of NMP, the mixture was stirred at 105° C. for about 1 hour, and NMPwas decanted at 105° C. The same operation was repeated four times intotal. After completion of decantation, lithium sulfide was dried at230° C. (i.e., a temperature equal to or higher than the boiling pointof NMP) for 3 hours in a nitrogen stream under normal pressure. Theimpurity content in the resulting lithium sulfide was measured.

The content of sulfur oxides which are lithium sulfite (Li₂SO₃), lithiumsulfate (Li₂SO₄), lithium thiosulfate (Li₂S₂O₃), and lithiumN-methylaminobutyrate (LMAB) was determined by ion chromatography. As aresult, the total content of the sulfur oxides was 0.13 mass %, and thecontent of lithium N-methylaminobutyrate (LMAB) was 0.07 mass %.

Li₂S thus purified was used in the following examples.

Example 1

The apparatus shown in FIG. 5 was used. A bead mill “Star MillMiniature” (0.15 l) (manufactured by Ashizawa Finetech Ltd.) was used asthe stirrer. 450 g of zirconia balls having a diameter of 0.5 mm wereused as the media. A glass reactor (1.5 L) equipped with a stirrer wasused as the reaction vessel.

A mixture prepared by adding 1080 g of dehydrated toluene (water content10 ppm or less) to 39.05 g (70 mol %) of Li₂S produced in ProductionExample 1 and 80.95 g (30 mol %) of P₂S₅ (manufactured by Aldrich) wasput in the reaction vessel and the mill.

The mixture was circulated at a flow rate of 400 mL/min using a pump,and the reaction vessel was heated to 80° C. Hot water was externallycirculated into the mill so that the liquid temperature was maintainedat 70° C., and the mill was operated at a circumferential speed of 10.9m/s. After reacting the mixture for 8 hours, the mixture wasvacuum-dried at 150° C. to obtain a white powder.

The Raman spectrum of the powder obtained was measured five times underthe following measurement conditions.

Measuring apparatus: Almega (manufactured by Thermo Fisher ScientificK.K.)

Laser wavelength: 532 nm, laser output: 10%, aperture: 25 μm (diameter),exposure time: 10 seconds, exposure count: 10, objective lens: ×100,resolution: high (2400 lines/mm)

FIG. 1 shows the average Raman spectrum of the five measurements. Ineach measurement, the peak at 330 to 450 cm⁻¹ in the Raman spectrum wasseparated to waveforms of the PS₄ ³⁻, P₂S₇ ⁴⁻, and P₂S₆ ⁴⁻ components(see FIG. 2) using waveform separation software (“GRAMS Al” manufacturedby Thermo SCIENTIFIC), and the waveform area ratio of each component wascalculated. The dotted line in FIG. 2 indicates the original peak. FiveRaman spectra were subjected to waveform separation, and the waveformarea ratio of each component was calculated. The average value and thestandard deviation of the waveform area ratio of the five Raman spectrawere calculated. The results are shown in Table 1.

The resulting powder was observed using an SEM at a magnification of3000 at which about one hundred particles were observed within the fieldof view (8 fields in total). The maximum particle size of the solidelectrolyte particles was 10 μm or less. FIG. 3 shows the SEM image.

The powder obtained was also subjected to DSC measurement under thefollowing conditions. The DSC measurement was performed using a system“MODEL DSC-7” (manufactured by Perkin Elmer). The powder was kept at 30°C. for 15 minutes, and then heated to 400° C. at 10° C./min. Theenthalpy of fusion was calculated from the peak area. It was found thatthe powder had a peak at 253° C. The enthalpy of fusion (ΔH) was 42.7J/g, and the peak half-width temperature was 4.3° C.

The ion conductivity of the powder obtained was also measured, and foundto be 1.2×10⁻⁴ S/cm.

The product reacted for 8 hours was put in an airtight container, andheated at 300° C. for 2 hours. The sample then was subjected to X-raydiffraction measurement. A peak was observed at 2θ=17.8, 18.2, 19.8,21.8, 23.8, 25.9, 29.5, and 30.0 deg attributed to the crystal phase ofLi₇P₃S₁₁. The ion conductivity of the powder was measured, and found tobe 1.8×10⁻³ S/cm.

The ion conductivity was measured by the following method.

Specifically, a tablet making machine was charged with the solidelectrolyte powder. A pressure of 4 to 6 MPa was applied to the solidelectrolyte powder to obtain a formed body. A mixed material (electrode)prepared by mixing carbon and the solid electrolyte in a weight ratio of1:1 was placed on each side of the formed body, and a pressure wasapplied to the formed body using the tablet making machine again toobtain a primary formed article. A pressure was applied to the primaryformed article during heating at 200° C. to obtain a formed body forconductivity measurement (diameter: about 10 mm, thickness: about 1 mm).The ion conductivity of the formed body was determined by AC impedancemeasurement. The ion conductivity measured at 25° C. was employed.

Example 2

A glass powder was produced, and the Raman spectrum of the glass powderwas measured in the same manner as in Example 1, except that thereaction time was changed to 12 hours. The results are shown in Table 1.

Example 3

A glass powder was produced, and the Raman spectrum of the glass powderwas measured in the same manner as in Example 2, except that xylene wasused as the reaction solvent. The results are shown in Table 1.

TABLE 1 Standard 1 2 3 4 5 Average deviation Example 1 PS₄ ³⁻ 29.4 25.427.6 28.4 27.9 27.7 1.5 P₂S₇ ⁴⁻ 57.7 62.3 59.3 59.3 57.9 59.3 1.8 P₂S₆⁴⁻ 13.0 12.3 13.1 12.3 14.1 13.0 0.8 Example 2 PS₄ ³⁻ 23.9 23.7 23.225.1 24.1 24.0 0.7 P₂S₇ ⁴⁻ 63.2 62.1 61.6 59.2 60.8 61.4 1.5 P₂S₆ ⁴⁻12.9 14.3 15.2 15.8 15.1 14.7 1.1 Example 3 PS₄ ³⁻ 27.1 25.2 23.9 21.425.9 24.7 2.2 P₂S₇ ⁴⁻ 58.8 59.1 60.3 60.8 57.8 59.4 1.2 P₂S₆ ⁴⁻ 14.115.7 15.8 17.8 16.3 15.9 1.3

Comparative Example 1

3.905 g (70 mol %) of Li₂S and 8.095 g (30 mol %) of P₂S₅ (manufacturedby Aldrich) were used as the raw materials. The powders were weighed ina dry box charged with nitrogen, and put in an alumina pot used for aplanetary ball mill together with alumina balls. The pot was thencompletely sealed in a state in which the pot was filled with nitrogengas. The pot was installed in a planetary ball mill, and the powderswere milled at a low speed (rotational speed: 85 rpm) for severalminutes in order to sufficiently mix the raw materials. The rotationalspeed was then gradually increased, and mechanical milling was performedat 370 rpm for a given time. The Raman spectrum of the resulting glasspowder was measured in the same manner as in Example 1.

Table 2 shows the area ratio of the Raman spectrum obtained inComparative Example 1. The standard deviation tended to decrease withthe passage of time. However, homogeneity obtained in the examples wasnot obtained even after the powders (raw materials) were milled for 280hours.

When observing the glass powder obtained using an SEM, large particleshaving a particle size of more than 20 μm were present. The ionconductivity of the glass powder obtained was 1.0×10⁻⁴ S/cm, and was1.3×10⁻³ S/cm when the glass powder had been heated at 300° C. for 2hours. A DSC chart was determined in the same manner as in Example 1. Apattern having two or more peaks was obtained.

TABLE 2 Ion Aver- Standard Sample species 1 2 3 4 5 age deviationMilling PS₄ ³⁻ 34.2 36.5 37.7 30.0 42.3 36.1 4.5 60 hr P₂S₇ ⁴⁻ 55.7 39.243.6 52.1 35.2 45.2 8.6 P₂S₆ ⁴⁻ 10.1 24.3 18.7 17.9 22.5 18.7 5.5Milling PS₄ ³⁻ 37.0 43.8 37.5 41.7 39.4 39.9 2.9 80 hr P₂S₇ ⁴⁻ 46.9 32.040.5 33.6 40.7 38.8 6.0 P₂S₆ ⁴⁻ 16.1 24.2 21.9 24.7 19.9 21.4 3.5Milling PS₄ ³⁻ 40.8 35.4 40.1 40.1 36.8 38.6 2.4 120 hr P₂S₇ ⁴⁻ 38.951.3 38.0 43.0 41.3 42.5 5.3 P₂S₆ ⁴⁻ 20.3 13.3 21.9 16.9 21.9 18.9 3.7Milling PS₄ ³⁻ 36.7 37.1 34.5 42.1 39.4 38.0 2.9 160 hr P₂S₇ ⁴⁻ 46.745.4 52.1 34.3 39.5 43.6 6.8 P₂S₆ ⁴⁻ 16.5 17.5 13.5 23.6 21.0 18.4 4.0Milling PS₄ ³⁻ 38.5 26.4 36.0 38.5 32.6 34.4 5.1 200 hr P₂S₇ ⁴⁻ 43.644.7 44.6 40.4 49.4 44.5 3.2 P₂S₆ ⁴⁻ 17.9 28.9 19.4 21.1 18.0 21.1 4.6Milling PS₄ ³⁻ 37.2 33.1 37.2 38.1 36.9 36.5 1.9 280 hr P₂S₇ ⁴⁻ 47.242.6 50.6 42.5 49.0 46.4 3.7 P₂S₆ ⁴⁻ 15.7 24.2 12.2 19.4 14.1 17.1 4.8

In Tables 1 and 2, each value was calculated using calculation softwareattached to the separation waveform software, or using Microsoft Excel.Each value was calculated to third to ten decimal places. A valuerounded off to one decimal place is listed in Tables 1 and 2.

INDUSTRIAL APPLICABILITY

Since the glass and the glass ceramic according to the invention exhibitexcellent homogeneity, the glass and the glass ceramic may suitably beused for a lithium secondary battery and the like.

Although only some exemplary embodiments and/or examples of theinvention have been described in detail above, those skilled in the artwill readily appreciate that many modifications are possible in theexemplary embodiments and/or examples without materially departing fromthe novel teachings and advantages of the invention. Accordingly, allsuch modifications are intended to be included within the scope of theinvention.

The documents cited in the specification are incorporated herein byreference in their entirety.

The invention claimed is:
 1. A method for producing a solid electrolyte,the method comprising: grinding raw materials comprising lithium sulfideand phosphorus sulfide in a hydrocarbon solvent.
 2. The method accordingto claim 1, comprising: the grinding raw materials comprising lithiumsulfide and phosphorus sulfide in the hydrocarbon solvent in a grinder,stirring a slurry comprising the raw materials and the hydrocarbonsolvent in a reaction vessel, and circulating the slurry through aconnecting pipe, wherein the method is carried out in an apparatuscomprising the grinder, the reaction vessel and the connecting pipe thatconnects the grinder and the reaction vessel.
 3. The method according toclaim 1, wherein the grinding is carried out with a rotary mill, a swingmill, a vibration mill, or a bead mill.
 4. The method according to claim1, wherein the hydrocarbon solvent is a saturated hydrocarbon, anunsaturated hydrocarbon or an aromatic hydrocarbon.
 5. The methodaccording to claim 1, wherein the phosphorus sulfide is phosphoruspentasulfide, and a molar ratio of the lithium sulfide to the phosphoruspentasulfide is from 50:50 to 80:20.
 6. The method according to claim 4,wherein the phosphorus sulfide is phosphorus pentasulfide, and a molarratio of the lithium sulfide to the phosphorus pentasulfide is from50:50 to 80:20.
 7. The method according to claim 2, wherein the grinderis a rotary mill, a swing mill, a vibration mill, or a bead mill.
 8. Themethod according to claim 2, wherein the grinder is a bead mill.
 9. Themethod according to claim 8, wherein the hydrocarbon solvent is anaromatic hydrocarbon.
 10. The method according to claim 8, wherein areaction temperature in the reaction vessel is from 60° C. to 300° C.11. The method according to claim 8, wherein a heat exchanger isprovided to the connecting pipe, the heat exchanger cools the slurrydischarged from the reaction vessel and then supplies the slurry to thegrinder.
 12. The method according to claim 9, wherein a heat exchangeris provided to the connecting pipe, the heat exchanger cools the slurrydischarged from the reaction vessel and then supplies the slurry to thegrinder.
 13. The method according to claim 2, wherein a grindingtemperature in the grinder is 20° C. or more and 90° C. or less.
 14. Themethod according to claim 2, wherein the hydrocarbon solvent is asaturated hydrocarbon, an unsaturated hydrocarbon or an aromatichydrocarbon.
 15. The method according to claim 2, wherein thehydrocarbon solvent is an aromatic hydrocarbon.
 16. The method accordingto claim 2, wherein the phosphorus sulfide is phosphorus pentasulfide.17. The method according to claim 16, wherein a molar ratio of thelithium sulfide to the phosphorus pentasulfide is from 50:50 to 80:20.18. The method according to claim 2, wherein a reaction temperature inthe reaction vessel is from 60° C. to 300° C.
 19. The method accordingto claim 2, wherein a heat exchanger is provided to the connecting pipe.20. The method according to claim 19, wherein the heat exchanger coolsthe slurry discharged from the reaction vessel and then supplies theslurry to the grinder.
 21. The method according to claim 1, furthercomprising: stirring a slurry comprising the raw materials and thehydrocarbon solvent.